N-((E)-1-(tert-butyldimethylsilyl)-3-(2-chlorophenyl)allylidene)-p-toluenesulfonamide | 1586870-01-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-((E)-1-(tert-butyldimethylsilyl)-3-(2-chlorophenyl)allylidene)-p-toluenesulfonamide
• CAS: 1586870-01-0
• 化学式: C₂₂H₂₈ClNO₂SSi
• 分子量: 434.074
• InChiKey: CRZAVYCUBOWHBZ-OIAJZWFVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.54
• 重原子数：
  28.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  46.5
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  N-((E)-1-(tert-butyldimethylsilyl)-3-(2-chlorophenyl)allylidene)-p-toluenesulfonamide 在 正丁基锂 、 (S)-2,2-dimethyl-N-(2-(4-methylpiperazin-1-yl)-1-phenylethyl)propan-1-amine 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 以27%的产率得到(E)-N-(1-(tert-butyldimethylsilyl)-3-(2-chlorophenyl)allyl)-p-toluenesulfonamide
  参考文献：
  名称：

  Enantioselective Synthesis of α-Silylamines by Meerwein–Ponndorf–Verley-Type Reduction of α-Silylimines by a Chiral Lithium Amide

  摘要：

  Meerwein-Ponndorf-Verley-type reduction of N-tosylsilylimines with chiral lithium amide 2 affords alpha-silylamines in high enantioselectivity. Since the enantioselectivity observed was inconsistent with our previously proposed chairlike six-membered transition structure, we performed density functional theory (DFT) calculations on transition states leading to (S)- and (R)-7a and (S)- and (R)-7e using an N-phenylsulfonyl derivatives 12 and 13 as model systems. Results of the calculations showed that the structures are considerably deformed from the chairlike form with steric repulsions between the 1'-methylene group and the imine-carbon substituents playing an important role in the control of the, enantioselectivity.

  DOI：

  10.1021/jo500441a
• 作为产物：
  描述：

  (E)-1-(tert-butyldimethylsilyl)-3-(2-chlorophenyl)prop-2-en-1-one 、 对甲苯磺酰胺 在 四氯化钛 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.5h， 以71%的产率得到N-((E)-1-(tert-butyldimethylsilyl)-3-(2-chlorophenyl)allylidene)-p-toluenesulfonamide
  参考文献：
  名称：

  Enantioselective Synthesis of α-Silylamines by Meerwein–Ponndorf–Verley-Type Reduction of α-Silylimines by a Chiral Lithium Amide

  摘要：

  Meerwein-Ponndorf-Verley-type reduction of N-tosylsilylimines with chiral lithium amide 2 affords alpha-silylamines in high enantioselectivity. Since the enantioselectivity observed was inconsistent with our previously proposed chairlike six-membered transition structure, we performed density functional theory (DFT) calculations on transition states leading to (S)- and (R)-7a and (S)- and (R)-7e using an N-phenylsulfonyl derivatives 12 and 13 as model systems. Results of the calculations showed that the structures are considerably deformed from the chairlike form with steric repulsions between the 1'-methylene group and the imine-carbon substituents playing an important role in the control of the, enantioselectivity.

  DOI：

  10.1021/jo500441a